With increasing concerns about the environmental impact of the chemical and polymer industries, there has been a steadily growing interest in the introduction of biodegradable polymers for a variety of applications, from fertilizer and seed-coating in agri-science, to biodegradable sutures, stitches and supports in medicine, to biodegradable plastic bags for the consumer market.1,2 Furthermore, due to the increasing costs and public concerns associated with petroleum feed stocks, alternative chemical sources, especially plant-derived materials are of increasing interest to industry for cost, resource security, and public relations purposes.3,4 With these factors in mind, polyglyoxylates, a class of degradable polymers, are of considerable interest. The properties of the materials can be modified not only by controlling the molecular weight of the resulting polymers, but also by modifying the identity of the ester side-chain and by incorporating them into block copolymers.5 Short polymers or oligomers are readily formed through the acid or base catalyzed polymerization of their parent glyoxylates in the presence of adventitious water. This has often made them difficult substrates for use in synthetic methodology,6 and the reversibility and instability of the resulting polymers has also limited their applications in materials science. However, they are particularly attractive as they ultimately degrade to corresponding alcohols and glyoxylic acid hydrate, an intermediate in the glyoxylate cycle, making them excellent biocompatible candidates for biomedical and agricultural applications.7 
Poly(methyl glyoxylate) (PMG) was first prepared by Monsanto for use as biodegradable detergent builder and complexing agent in 1979.8,9,10 However, because of the low ceiling temperature of this polymer, it has a very short half-life at room temperature, greatly limiting possible applications. The stability of PMG can, however, be improved greatly when it is properly end-capped,11 and investigations into the thermal stability and degradation kinetics of PMG were all completed two decades ago.12,13 Poly(ethyl glyoxylate) (PEtG) was successfully synthesized by the Burel group through anionic polymerization in 2003.14 Similar to PMG, PEtG is readily degradable, but the reduced toxicity of ethanol relative to methanol suggests that PEtG has increased potential in medical, pharmaceutical, and environmental applications.15,16,17 
As both methyl glyoxylate and ethyl glyoxylate can easily be polymerized, and both polymers show different physical properties (the former being a glassy solid up to 25° C., while the latter is a white, sticky, rubber-like solid at room temperature), the potential physical properties of other members of this family demand investigation. The difficulties in the preparation and isolation of higher-order glyoxylates in sufficient purity for synthetic methodology, let alone the very high purities required for polymerization, have limited research interest and investigations into their utility. However, a general high conversion and high purity synthetic approach should allow access to a wide variety of different glyoxylates and potentially a wider variety of physical properties.